CN109312134A - With the improved ABS moulding compound of crack resistance and chemical resistance and application thereof - Google Patents

With the improved ABS moulding compound of crack resistance and chemical resistance and application thereof Download PDF

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Publication number
CN109312134A
CN109312134A CN201780038328.4A CN201780038328A CN109312134A CN 109312134 A CN109312134 A CN 109312134A CN 201780038328 A CN201780038328 A CN 201780038328A CN 109312134 A CN109312134 A CN 109312134A
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weight
copolymer
component
graft
styrene
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CN109312134B (en
Inventor
J·米凯利斯·德华斯孔遂洛
N·尼斯内
K·H·李
G·米歇尔斯
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Ineos Styrolution Group GmbH
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Ineos Styrolution Group GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C08F212/10—Styrene with nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00—General constructional features
    • F25D23/06—Walls
    • F25D23/065—Details
    • F25D23/066—Liners
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2055/00—Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups B29K2023/00 - B29K2049/00, e.g. having a vinyl group, as moulding material
    • B29K2055/02—ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/01—High molecular weight, e.g. >800,000 Da.
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Thermoplastic composition is advantageously used for the region of hydrogen-containing fluoroolefin, including component A, B, the ABS graft rubber A that C and D:10 to 35 weight % is obtained by emulsion polymerization, 50 to 75 weight %SAN copolymer B, the ABS graft rubber copolymer D of the copolymer weight of C and 4 to 20 % from ethylene and (methyl) acrylic acid C1-C6 Arrcostab of 4 to 20 weight % obtained by bulk polymerization.

Description

With the improved ABS moulding compound of crack resistance and chemical resistance and application thereof
Invention description
The present invention relates to ABS moulding compounds, show in the presence of olefinic unsaturation foaming agent such as HF hydrocarbon (HFO) The environmental stress crack resistance improved out.The purposes that the invention further relates to them in hydrogen-containing fluoroolefin region and as cooling The purposes of liner layer in device.
For the liner of thermal forming device (such as refrigerator), styrol copolymer, especially ABS resin are usually preferred material Material, because of its performance for more balancing: intensity, toughness (impact resistance), appearance (gloss and color), chemical resistance, processability And price.The ABS of sheet material extrusion grade can show deep drawn ability in thermoforming operations, can provide in assembling and use persistently Intensity and toughness, for for foodstuff article tool then have high glaze, antipollution and chemical resistance.
Document KR-A 2006131373 discloses a kind of heat-proof ABS moulding compound, and it includes 20 to 35 parts by weight ABS graft rubber (A), 0.1 to 10 parts by weight ethylene-(methyl) alkyl acrylate copolymer (such asAC)) (B) and the mixture of two kinds of san copolymers of 84.9 to 55 parts by weight (C, one of which be c1 (long-chain) another kind be c2 (branch Chain), AN content is 20 weight %.Above-mentioned abs polymer blend is used for outdoor application (automobile component, construction material etc.), right In anti-insecticide and detergent, improved chemical resistance and crack resistance are shown.Gather however, the document does not relate to ABS Application of the polymer composition in cooling device.
Refrigerating industry is thermally shielded between external metal safe and Inner plastic lining using polyurethane foam.Polyurethane needs Foaming agent is wanted to generate foam.The selection of foaming agent is a complicated problem, depends on many factors, including thermal conductivity, at This, flammable, toxicity and environmental factor (such as ozone-depleting and potential global warming trend).As refrigerator liners, ABS resin The insulator of foam in place can be also contacted during assembly.The insulation of foam in place generally produces a kind of chemical foaming agent (chemistry The mixture of product or different chemical product) shove, so as to make insulating materials (such as polyurethane) foam.
When ABS pad is exposed to foaming agent, ABS resin must be to provide the side of chemical resistance to the foaming agent applied Formula design and composition.Otherwise, ABS material can be made to degenerate when contacting with lining, leads to its rupture.So far, it has invented Several ABS compositions, to common foam foaming agent such as chlorofluorocarbons (CFC), hydrochlorofluorocarbons (HCFC), hydrofluorocarbon (HFC) and Hydrocarbon (such as pentamethylene) shows good anti-stress cracking.
US 2008/0093578 discloses a kind of thermoplastic resin composition for refrigerator, and it includes poly- by lotion The ABS graft copolymer resin (A) obtained is closed, (it includes by making polybutadiene and acrylonitrile and benzene for styrol copolymer (B) Ethylene copolymer and the copolymer (b1) prepared and the copolymer (b2) by polybutadiene and styrene copolymerized preparation) and SAN it is total Polymers (C).The resin combination has the anti-stress cracking for HCFC.
About the potential trend of environmental factor, especially global warming, a kind of foaming agent-containing alkene is developed " forth generation " foaming agent.These so-called HFO (HF hydrocarbon, such as anti-form-1-chloro-3,3,3 ,-trifluoropropene, trade namesLBA, Honey-well or1233zd, Arkema and (Z) -1,1,1-4,4,4- hexafluorobutenes, FHO-1336mzz-Z trade name1100, Chemours) unsaturation is easy to them in an atmosphere It decomposes in several days rather than in the centuries, to reduce harmful global warming to the maximum extent.However, although these HFO are sent out Infusion has the advantages that, but for the ABS material in refrigerator lining, they seem to be easier to cause its environmental stress crack And damage.
US2014/019090978 describes the refrigeration machine with polyurethane foam insulation, and wherein foaming agent basically comprises 1- Chloro- 3,3,3- trifluoro propene.Preferably, the liner layer of refrigerator is largely formed by high impact polystyrene (HIPS).In lining It at least can partly contain other suitable materials such as GPPS, styrol copolymer, such as styrene-butadiene block copolymer, ASA, ABS, polyolefin, (methyl) acrylate, such as PMMA, PC, PVC, PET and their mixture.But it is provided all Embodiment in, only used HIPS.
Application for this foaming agent, needing used ABS resin, (acrylonitrile-butadiene-styrene (ABS)-is altogether Ionomer compositions), it is capable of providing major part advantageous property known to ABS material, such as intensity, toughness (impact resistance), appearance (light Pool and color), machinability and price, but its mixture to alkene foaming agent or containing these foaming agents is especially needed to have Higher resistance to stress Fractured.
Problem to be solved by this invention is the serious environmental stress cracking caused by ABS resin as the presence of HFO Property and its influence to the ABS resin liner service life in cooling device.
It is an object of the present invention to provide the ABS resin compositions for being suitable for cooling device liner, show ABS material The known most of advantageous property of material, and the resistance to environment for especially showing to improve in the presence of olefinic unsaturation foaming agent is answered In power cracking behavior (ESCR) performance, the especially environment existing for HF hydrocarbon (HFO).Composition used in the present invention is shown This excellent performance.
One aspect of the present invention is the purposes in a kind of thermoplastic composition region existing for hydrogen-containing fluoroolefin, It includes component A, B, C and D (if present) or by component A, B, C and D (if present):
(A) at least one graft rubber copolymer A of 10-35 weight %, consisting of the following to be obtained through emulsion polymerization:
(a1) it is based on (A), at least one graft base (a1) of 30 to 90 weight % comes from:
(a11) it is based on (a1), at least one diene of 70 to 98 weight %, especially 1,3-butadiene, and
(a12) it is based on (a1), at least one monomer selected from the group below of 2 to 30 weight %: styrene, Alpha-Methyl benzene second Alkene, acrylonitrile, methacrylonitrile and methyl methacrylate, especially styrene；With；
(a2) it is based on (A), the graft (a2) of 10 to 70 weight % is grafted in graft base and comes from:
(a21) it is based on (a2), at least one vi-ny l aromatic monomers of 65 to 95 weight %, especially styrene,
(a22) it is based on (a2), the acrylonitrile and/or methacrylonitrile of 5 to, 35% weight %, preferably acrylonitrile, and
(a23) it is based on (a2), at least one monomer selected from the group below of 0 to 20 weight %: C1-C4- (methyl) acrylic acid Arrcostab, maleic anhydride, N-phenylmaleimide, N- N-cyclohexylmaleimide and (methyl) acrylamide；
(B) at least one copolymer B of 50 to 70 weight %, comes from:
(b1) (B), at least one vi-ny l aromatic monomers of 50 to 95 weight %, optimization styrene or Alpha-Methyl benzene are based on Ethylene, more preferable styrene, and:
(b2) it is based on (B), the acrylonitrile and/or methacrylonitrile of 5 to 50 weight %, preferably acrylonitrile, and:
(b3) it is based on (B), one or more monomers as described in (a23) of 0 to 20 weight %；
(C) at least one elastic block copolymer C of 4 to 20 weight %, comes from:
(c1) it is based on (C), the ethylene of 70 to 91 weight %,
(c2) it is based on (C), at least one (preferably a kind of) (methyl) acrylic acid C1-C6 Arrcostab of 9 to 30 weight % is excellent Select C1-C6 alkyl acrylate, more preferable methyl acrylate, ethyl acrylate and/or n-butyl acrylate, most preferably acrylic acid Methyl esters and/or ethyl acrylate, especially methyl acrylate, and
(c3) it is based on (C), other comonomers that at least one of 0 to 15 weight % can be copolymerized with (c1) and (c2) are excellent Choosing is selected from: carbon monoxide, alpha-olefin such as propylene and/or (methyl) acrylic acid, (methyl) glycidyl acrylate；
(D) at least one graft rubber copolymer D obtained by bulk polymerization of 0 to 20 weight %, it is consisting of the following It obtains:
(d1) it is based on (D), at least one graft base d1 of 10 to 25 weight % comes from:
(d11) it is based on (d1), at least one diene of 75 to 100 weight %, especially 1,3-butadiene, and
(d12) (d1), at least one vi-ny l aromatic monomers of 0 to 25 weight %, optimization styrene or Alpha-Methyl are based on Styrene, more preferable styrene, and；
(d2) it is based on (D), the graft (d2) of 75 to 90 weight % is grafted in graft base and comes from:
(d21) be based on (d2), 68 to 82 weight %, preferably 70 to 80 weight %, at least one vi-ny l aromatic monomers, Optimization styrene or α-methylstyrene, more preferable styrene,
(d22) be based on (d2), 18 to 32 weight %, preferably 20 to 30 weight %, acrylonitrile or methacrylonitrile, preferably Acrylonitrile, and
(d23) it is based on (d2), 0 to 20 weight %'s is one or more such as (a 23) described monomer；
The summation of wherein component A, B, C and D are weight 100%.
According to the present invention, term " substantially polymerize " (mass polymerization) and refers to ontology or polymerisation in solution or outstanding Then floating polymerization continues final wherein polymerization starts as ontology or polymerisation in solution as previously described after suspending in water Conversion.
According to the present invention, above-mentioned moulding compound is preferred for preparing the liner of cooling equipment (especially refrigerator).
Term " weight % " is identical as " % weight ".Term " pbw " is identical as " parts by weight ".
The minimum of optional components D is 0.01 weight %, preferably 0.05 weight %, more preferable 0.10 weight %.If There are optional components D in the thermoplastic composition, and/or further define the amount of component A and/or C, then component B Amount be set in a value in given range so that the amount of component A to D is added up up to 100% weight.
Above-mentioned thermoplastic composition used according to the invention can further include optional component E and/or F.
Component E is at least one inorganic additive E for being selected from phyllosilicate (E1) and nanometer calcium carbonate (E2).Based on 100 The composition of parts by weight being made of component A, B, C and D, the dosage of component E can be 0.01 to 10 parts by weight.
Component F is other at least one additives and/or processing aid F.Based on 100 parts by weight by component A, B, C and D The composition of composition, the dosage of component F can be 0.01 to 20 parts by weight.
If the thermoplastic composition contains optional component E and/or F, the respective minimum of component E and F Preferably 0.05 parts by weight, more preferable 0.10 parts by weight, the composition being made of component A, B, C and D based on 100 parts by weight.
Preferably, thermoplastic composition used according to the invention, component A, B, C and D comprising following content, or It is made from it:
(A): 18 to 28 weight %；
(B): 55 to 75 weight %；
(C): 6 to 15 weight %；
(D): 0 to 15 weight %；
Wherein component A, B, C and D are defined as described above.
It is highly preferred that thermoplastic composition used according to the invention, component A, B, C and D comprising following content, Or it is made from it:
(A): 18 to 28 weight %；
(B): 55 to 70 weight %；
(C): 6 to 15 weight %；
(D): 0 to 15 weight %；
Wherein component A, B, C and D are defined as described above.
It is further preferred that according to the present invention use thermoplastic composition, the component comprising following content
A, B, C and D, or be made from it:
(A): 10 to 35 weight %；
(B): 50 to 75 weight %；
(C): 4 to 20 weight %；
(D): 4 to 20 weight %；
Wherein component A, B, C and D are defined as described above.
Moulding compound using component A, B, C and the D composition by above-mentioned limited amount is particularly preferred.
The moulding compound that the further preferred present invention uses, by component A, B, C, the component of the parts by weight of D and 1 to 20 F (composition being made of component A, B, C and D based on 100 parts by weight) composition.
The moulding compound that the further preferred present invention uses is made of component A, B, C, D and E, wherein being based on 100 The composition of parts by weight being made of component A, B, C and D, the content of E are 0.01 to 10 parts by weight, preferably 0.01 to 8 parts by weight, The component of more preferable 0.01 to 5 parts by weight.
The moulding compound that the further preferred present invention uses is made of component A, B, C, D, E and F, wherein being based on The composition of 100 parts by weight being made of component A, B, C and D, the content of F are 1 to 20 parts by weight, and the content of E is 0.01 to 10 Parts by weight, preferably 0.01 to 8 parts by weight, the component of more preferable 0.01 to 5 parts by weight.
Another aspect of the present invention is the thermoplastic composition applied to hydrogen-containing fluoroolefin region, includes following content Component A, B, C and D, or be made from it:
(A): 10 to 35 weight %；
(B): 50 to 75 weight %；
(C): 4 to 20 weight %；
(D): 4 to 20 weight %；
The definition of wherein component A, B, C and D are with above-described for the identical of thermoplastic composition.
Above-mentioned novel thermoplastic moulding compound also may include the optional components E and/or F of above-mentioned amount.For using basis Thermoplastic composition of the invention and the component A, B, C provided, D and being defined for optional components E and F are equally applicable to Thermoplastic composition itself.The moulding compound of aforementioned present invention is preferably used to prepare cooling equipment (especially refrigerator) Liner.
Moulding compound of the invention preferably comprises following component, or is grouped as by following group:
(A): 18 to 28 weight %；
(B): 55 to 70 weight %；
(C): 6 to 15 weight %；
(D): 6 to 15 weight %；
Wherein component A, B, C and D are defined as described above.
Moulding compound more preferably as defined above includes following component, or is grouped as by following group:
(A): 18 to 28 weight %；
(B): 55 to 69 weight %；
(C): 6 to 15 weight %；
(D): 6 to 15 weight %；
The summation of wherein component A, B, C and D be 100 weight %, and based on 100 parts by weight by component A, B, C and D group The composition being grouped as further includes the component F of 1 to 20 parts by weight.
Another aspect of the present invention is that the thermoplastic composition is applied to prepare cooling device (especially refrigerator) The purposes of liner.
Component A (graft rubber copolymer A)
At least one graft rubber copolymer A is used as impact modifier and forms a soft phase, glass transition Temperature Tg < 0 DEG C, preferably < -20 DEG C, particularly preferably < -40 DEG C.Glass transition temperature is used by dynamic mechanical analysis (DMA) The frequency measurement of 1Hz.
At least one graft copolymer A according to the present invention, is preferably made of following components:
(a1) it is based on (A), 40 to 90 weight %, preferably 45 to 85 weight %, particularly preferred 45 to 75 weight % is at least One graft base a1, is made up of preparation:
(a11) be based on (a1), 80 to 98 weight %, preferably 85 to 97 weight %, at least one diene, preferably 1,3- fourth Diene, and
(a12) be based on (a1), 2 to 20 weight %, preferably 3 to 15 weight %, at least one monomer, optimization styrene； With；
(a2) be based on (A), 10 to 60 weight %, preferably 15 to 55 weight %, particularly preferred 25 to 55 weight %, grafting Object a2 is grafted in graft base and comes from:
(a21) be based on (a2), 65 to 80 weight %, especially 65 to 75 weight %, at least one aromatic vinyl list Body (a21), especially styrene, and
(a22) be based on (a2), 20 to, 35% weight %, especially 25 to 35 weight %, acrylonitrile and/or methyl-prop Alkene nitrile (a22), preferably acrylonitrile, and
(a23) it is based on (a2), at least one monomer (a23) of 0 to 20 weight %；
Diene a11 is preferably 1,3-butadiene and/or isoprene, more preferably 1,3-butadiene.Comonomer a12 is excellent It is selected as styrene.Vi-ny l aromatic monomers a21 is preferably styrene and/or α-methylstyrene, more preferably styrene.Copolymerization Monomer a22 is acrylonitrile and/or methacrylonitrile, preferably acrylonitrile.Other comonomer a23 is that at least one is selected from the group Monomer: C1-C4- (methyl) alkyl acrylate, maleic anhydride, N-phenylmaleimide, N- N-cyclohexylmaleimide (methyl) acrylamide, preferably C1-C4- (methyl) alkyl acrylate and maleic anhydride.Preferably, comonomer is not present a23。
The weight average particle diameter Dw of at least one graft base a1 of graft copolymer A is usually 0.15 μm to 0.80 μm, preferably 0.15 μm to 0.50 μm, particularly preferred 0.20 μm to 0.50 μm, most preferably 0.25 μm to 0.40 μm.
Can be used have it is single, it is double, three or multimodal size distribution one or more graft copolymer A. weight average particle diameter Dw It can be measured by ultracentrifuge (referring to W.Scholtan, H.Lange:Kolloid Z.u.Z.Polymere 250, pp.782 To 796 (1972)) or disc centrifuge DC measurement (by CPS Instruments Inc. manufacture) revolving speed be 24,000 revs/min It is measured under clock.Partial size can also be measured by static light scattering (referring to A.Schmidt in Houben-Weyl, Methoden Der Organischen Chemie, Georg Thieme Verlag, Stuttgart, 1987, volume E20, pp.238- 248) this method and the method difference of front two, cannot provide the information about size distribution.About the definition of average particle size Dw, Referring to: G.Lagaly, O.Schulz, R.Zimehl: " dispersion and lotion: introduce the colloidization of finely divided material, including clay pit Object ", Darmstadt:SteinkopfVerlag 1997, ISBN 3-7985-1087-3, page 282, formula 8.3b.
Preferred diene rubber (graft bases a1) and graft copolymer A are described in EP-B 0993476, WO 01/62848 In WO 2012/022710 (especially the 23-28 pages).
The method for preparing graft copolymer A is known to the skilled in the art and is described in the literature.According to this Invention is grafted basic (a1) and graft copolymer A and is obtained by free-radical emulsion polymerization (referring to 993476 B of EP, WO 01/ 62848 and WO 2012/022710).
The suitable temperature of emulsion polymerisation process is usually 20 to 100 DEG C, and preferably 30 to 90 DEG C.As emulsifier, can make With conventional emulsifier, such as the alkali metal salt of alkyl or alkyl aryl sulphonic acid, alkyl sulfate, there is 10-30 carbon atom Higher fatty acid salt, sulfosuccinate, ether sulfonate or the rosin soap from different natural materials.Optimizing alkyl sulfonic acid or tool There are the alkali metal salt of the fatty acid of 10-18 carbon atom, especially its sodium salt and sylvite.
Further preferred resin or rosin acidic group emulsifier, the especially basic salt of rosin acid.The salt of resin acid is also referred to as Rosin soap.Example includes basic soap, such as the sodium salt from disproportionation and/or dehydration and/or hydration and/or partially hydrated gum rosin Or sylvite, wherein the content of dehydroabietic acid is at least 30 weight %, preferably at most 1 abietic acid content.Weight %.This Outside, the sodium salt or sylvite of basic soap such as high resin or tall oil can be used, wherein the content of dehydroabietic acid is preferably at least 30 weight %, the content of rosin acid is preferably at most 1 weight % and the content of fatty acid is preferably smaller than 1 weight %.Above-mentioned emulsification The mixture of agent can also be used for production starting rubber latex.Use basic soap as from disproportionation and/or dehydration and/or hydration And/or the sodium or sylvite of partially hydrated gum rosin, wherein the content of dehydroabietic acid is at least weight %, the content of rosin acid It is up to weight % to be advantageous.
Based on the amount for being used to prepare graft bases a1 monomer, the general dosage of emulsifier is 0.5 to 5 weight %, especially 0.5 to 4 weight %.
When preparing dispersion, it is preferable that a certain amount of water is used to make final dispersion that there are 20 to 50 weight % Solid content.
To cause polymerization, radical initiator is that suitably, it is decomposed under selected reaction temperature, i.e., just by heating Those of those of can decompose, and can decompose in the presence of redox system.Polymerization initiator used is preferably that A little polymerization initiators for forming free radicals, such as peroxide, preferably peroxysulphate (such as sodium peroxydisulfate or potassium peroxydisulfate) and Azo-compound such as azodiisobutyronitrile.Redox system can also be used, is based particularly on the oxidation of hydroperoxides also Substance system, such as cumene hydroperoxide or tert-butyl hydroperoxide, in addition reducing agent such as sucrose, glucose and ferrous iron.
Based on the amount of grafting base monomer a11 and a12, the dosage of polymerization initiator is usually 0.05 to 1 weight %, preferably 0.1 to 1 weight %.
Total amount can be added at one time in reaction mixture by polymerization initiator and emulsifier when reacting beginning, or It is divided into several parts to be intermittently charged when starting with time interval that subsequent one or more is specified.Continuous addition can also follow Gradient, the gradient can be rise or fall and can be it is linear or index, or gradually.
In addition it is possible to use molecular weight regulator, such as ethylhexyl thioglycolic acid esters, just or tert-dodecylmercaotan With other mercaptan, terpineol and two poly alpha methylstyrenes or other the suitable compounds for adjusting molecular weight.
The addition manner of polymerization initiator and emulsifier as described above, molecular weight regulator can be added in batch or continuously instead It answers in mixture.
For the pH value kept constant, preferably 6 to 12.5, preferably 7 to 12.0, buffer substance such as Na can be used2HPO4/ NaH2PO4, sodium bicarbonate, sodium carbonate or the buffer based on citric acid/citrate.Regulator and buffer substance are with common Amount uses.
In an especially preferred embodiment, graft bases a1's and monomer a21 and a22 and optional a23 In grafting process, hydroperoxides and reducing agent is added, and ferrous iron is added simultaneously.
Those skilled in the art can choose the type of polymerizing condition, especially emulsifier and other reagent and additive in polymerization, quantity And dosage, so that rubber latex (graft bases) a1 of obtained graft copolymer A has average grain diameter (i.e. weight average particle diameter Dw) It is 0.15 μm to 0.80 μm, preferably 0.15 μm to 0.60 μm, particularly preferred 0.20 μm to 0.50 μm, most preferably 0.25 μm to 0.40 μm。
In the case where monomodal grit distribution, the polymer particle partial size Dw of graft base a1 is preferably 0.20 μm to 0.50 μm, more preferable 0.25 to 0.40 μm.
It is also an option that polymerizing condition, so that the polymer beads of graft bases a1 have two peaks within the above range, Three peaks or multimodal size distribution.Two peaks, three peaks or multimodal grain can be realized by being grafted (part) agglomeration of base particle a1 Degree distribution.
Moreover it is preferred that two peaks in order to realize graft rubber copolymer A, three peaks or multimodal size distribution, it can be with logical Normal mode prepares different the graft base a1-1, a1-2 etc. of two or more weight average particle diameters Dw apart from each other, and with institute The mixing ratio needed mixes the graft base a1-1, a1-2 etc..
Advantageously, graft base a1 is prepared in a usual manner first, it is then respectively by it, attached with two or more batches It is polymerized to, to obtain two or more different graft bases a1-1, a1-2 etc. (their partial size Dw is different).It then will grafting Object a2 is grafted on the mixture of described (agglomeration) graft bases a1-1, a1-2 etc..It is preferable to use have two peak size distributions Graft rubber copolymer (A), prepared by the coarse grained mixture of the graft base a1-1 fine grained and a1-2 of agglomeration.Grafting Substrate a1-1 partial size Dw is 0.15 μm to 0.30 μm, preferably 0.15 μm to 0.25 μm；The partial size Dw of graft base a1-2 is 0.40 μ M to 0.80 μm, preferably 0.45 μm to 0.60 μm.The mixing ratio of graft base a1-1 and a1-2 are preferably 50/50 to 90/10.
According to a specific embodiment, graft bases a1 can in the presence of latex fine crushing by polymerized monomer a11 and A12 prepares (i.e. so-called " seed latex " polymerization).The latex can obtain, can be by the elastomer polymer of formation monomer Or it is prepared by other monomers as described above.Suitable seed latex is made of such as polybutadiene or polystyrene.
In seeding polymerization, polymer fine crushing, preferably polybutadiene are usually prepared first, as seed latex, then Particle by the seed latex further with the monomer polymerization Cheng Geng great containing butadiene (referring to Houben-Weyl, " organises Method, macromolecular substances ", first, page 339 (1961), Thieme Verlag, Stuttgart).It is preferable to use seed lots It handles (seed batch process) or is carried out using seed feeding (seedfeed process) method.Preferred grafting base Matter a1 and graft copolymer A can be obtained by seeding polymerization technology described in document WO2012/022710 A1.
In another preferred embodiment, graft base a1 is produced with so-called feeding method.In the method, it mentions For a certain proportion of monomer a11 and a12 and start to polymerize, be then added in the course of the polymerization process remaining monomer a11 and a12 (" into Expect part ") it is used as feeding.
It feeds parameter (gradient shape, amount, duration etc.) and depends on other polymerizing conditions.Radical initiator and emulsification The addition of agent is as previously described.Preferably, in feeding method, it is based on a1, the ratio for starting the monomer provided is at most 50 weights Measure %, preferably up to 40 weight %.Preferably, the rest part of monomer a11 to a12 is in 1 to 18 hour, and especially 2 to 16 Hour, feeding in more preferable 4 to 12 hours.
In second stage, rubber latex agglomeration.This can be by adding the dispersion of acrylate copolymer as agglomeration Agent is completed.It is preferred that made of the C1-C4 Arrcostab (preferably ethyl acrylate) and 0.1-10 weight % monomer of acrylic acid altogether The dispersion of polymers, the monomer form polar polymer, such as acrylic acid, methacrylic acid, acrylamide or Methacrylamide, N- methylol methacrylamide or n-vinyl pyrrolidone.Particularly preferably by 96% ethyl acrylate and 4% methyl Copolymer made of acrylamide.Agglomeration dispersion optionally contains one or more above-mentioned acrylate copolymers.
Concentration for acrylate copolymer in the dispersion of agglomeration is usually 3-40 weight %.For agglomerate, base In 100 parts of rubber latexs, use 0.2 to 20, the agglomeration dispersion of preferably 1 to 5 parts by weight, the parts by weight are based on solid and contain Amount calculates.Agglomeration is carried out by the way that agglomeration dispersion to be added in rubber.Adding rate is typically not critical, it usually needs about 1 To 30 minutes, temperature was between 20 to 90 DEG C, preferably between 30 to 75 DEG C.
Particularly preferred rubber latex (graft bases a1) and sour (preferred anhydrides, more preferable acetic anhydride) agglomeration (referring to WO2012/022710, the 9-10 pages).Preferably, rubber latex a1 and the acid-mixed are closed, and after the completion of reunion, preferably Again stable with alkali, the preferred potassium hydroxide solution of alkali used individually or with emulsifier solution such as sodium naphthalene sulfonate or potassium first is condensed Object or rosin soap share.Be preferred for again it is stabilized be potassium hydroxide solution and sodium naphthalene sulfonate or potassium formaldehyde condensation products or pine The combination of perfumed soap.
Preferably, above-mentioned agglomeration uses acetic anhydride.But it is also possible to use other organic acid anhydrides.Acetic acid can also be used The mixture or organic acid anhydride and acetic acid of acid anhydride and acetic acid or the mixture of other carboxylic acids.
Once agglomeration is completed, the rubber latex of agglomeration is preferably again stable with alkali.It is molten that alkali used can be potassium hydroxide Liquid, or preferably it merges with the formaldehyde condensation products of emulsifier solution such as sodium naphthalene sulfonate or naphthalene sulfonic acid potassium or rosin soap and makes With so that pH value is preferably greater than 7.5.Other alkaline solutions, such as sodium hydroxide solution can be used, although this is not preferred 's.
According to preferred embodiment, starting rubber latex is provided first, it is preferable that by the way that water is added by the solid of the latex Content is adjusted to 25 to 45 weight %.The temperature for originating rubber latex (preferably mixing with water) can be at 0 DEG C to 70 DEG C, and preferably 0 DEG C To 60 DEG C, adjusted in particularly preferred 15 DEG C to 50 DEG C of larger range.
It is preferred that at such a temperature, the mixture of the preferred acetic anhydride and water that are mixed with will be passed through under good admixture It is added in starting rubber latex.Acetic anhydride-aqueous mixtures are added and mix should be in most two minutes with starting rubber latex It carries out, to keep coagulation as few as possible to be formed.It, can by the measure although the formation of coagulation cannot be avoided completely With the amount of advantageously limit coagulation object.Based on the amount of solid of used starting rubber latex, coagulation is significant less than 1 weight Measure %, usually less than 0.5 weight %.
Preferably, acetic anhydride-aqueous mixtures mixing ratio used in agglomeration step be 1:7.5 to 1:40, preferably 1: 10 to 1:30, more preferable 1:15 to 1:30.When acetic anhydride-aqueous mixtures are added, the rubber fine grained in rubber latex is originated Reunion initially form biggish rubber grain, and 5 to completing (depend on temperature adjusted) after sixty minutes.At this stage It does not stir or mixed rubber latex, when the pH value of the hydrolysis of the acetic anhydride of whole amount and rubber latex does not decline further, Agglomeration (i.e. the increase of rubber particle size) stops.In order to further stabilize, preferably by potassium hydroxide solution or preferably with Foregoing emulsifier solution combination, is carefully added in rubber latex and mixes with rubber latex, so that rubber latex PH value be at least 7.5.
According to another preferred embodiment, (every 100 parts of startings rubber latex is based on by the way that 0.1 to 5 parts by weight are added Amount of solid) acetic anhydride carry out agglomeration step.Here, starting rubber latex amount of solid refers to solid content (in drying box Evaporation sample, 180 DEG C of temperature, 25 minutes time) it is preferably 25 to 45 weight %, more preferable 30 to 45 weight %, particularly preferably 35 to 45 weight %.
In addition, being also possible by pressure or freezing agglomeration (i.e. pressure or freezing agglomeration).These methods are this fields Known to technical staff.
Graft bases a1 can be adjusted in principle with usual manner known in the art by using suitable reaction condition Gel content, such as high reaction temperature and/or polymerization be until high conversion, and is optionally added into crosslinking substance), can obtain Obtain high gel content；On the contrary, low reaction temperatures and/or terminating polymerization reaction before high-crosslinking-degree occurred, and optionally It is added molecular weight regulator (such as n-dodecyl mercaptan or tert-dodecylmercaotan), then can obtain low-gel content.
In general, carrying out the polymerization of graft bases a1 by selection reaction condition, can obtain with specific cross-linked state Graft bases a1.These reaction conditions are reaction basic parameter, especially reaction temperature and time, monomer, regulator, free radical The ratio of initiator, and, for example, in fill process, feed rate and amount and the time that regulator and initiator is added.
The cross-linked state of graft bases a1 can be measured by gel content, and gel is reaction product, because it is crosslinking , therefore do not dissolve in specific solvent.Gel content can be measured in toluene by line cage method (referring to Houben-Weyl, " to be had Chemical machine method, macromolecular substances ", part 1, page 307 (1961), Thieme Verlag Stuttgart).
Common, the gel content for graft bases a1 of the invention is 60-98%, preferably 65-98%, more preferable 70- 97%, most preferably 75-95%.Preferably, the gel content of graft bases a1 is 70 to 97%, preferably 75 to 95%, and is coagulated Swellbility of the glue in toluene is in the range of 15 to 35, preferably in the range of 18 to 33.
The preparation of the graft a2 that is grafted on graft base a1 can prepare identical condition with graft base a1 Lower progress can prepare graft a2 in one or more processing steps in this way.Prepare the further details of graft copolymer A It is described in DE1260135 and WO2012/022710.
The graft polymerization of monomer a21, a22 and a23 are also carried out with free-radical emulsion polymerization technology.It can with grafting base It is carried out in the identical system of the polymerization of matter a1, and other emulsifier and initiator can be added.
These need not be identical as the emulsifier or initiator for being used to prepare graft bases a1.For emulsifier, initiator is adjusted The selection of agent etc. is saved, the description prepared in graft bases a1 is equally applicable.Monomer mixture to be grafted can once be added instead It answers in mixture, or is added several times in batches, or be preferably continuously added in the course of the polymerization process.
In the grafting process of graft bases, the non-grafted polymers of monomer a21 to a22 can be generated, their amount is also counted It calculates in the weight of component A, usually 10 to 50% (being based on a2).
Preferably, it using at least one graft copolymer A, is obtained by following emulsion polymerizations:
(a1) it is based on (A), 40 to 90 weight %, preferably 45 to 85 weight %, particularly preferred 45 to 75 weight % is at least One graft base a1, is made up of preparation:
(a11) be based on a1,80 to 98 weight %, preferably 85 to 97 weight %, at least one diene, preferably 1,3- fourth two Alkene, and
(a12) be based on a1,2 to 20 weight %, preferably 3 to 15 weight %, styrene；With；
(a2) be based on (A), 10 to 60 weight %, preferably 15 to 55 weight %, particularly preferred 25 to 55 weight %, grafting Object (a2), is grafted on graft base a1, and come from:
(a21) be based on a2,65 to 80 weight %, especially 65 to 75 weight %, styrene, and
(a22) be based on a2,35% weight % of 20to, especially 25 to 35 weight %, acrylonitrile.
Component B
Component B forms hard phase, has > 20 DEG C of a glass transition temperature Tg, and Tg is with dynamic mechanical analysis (DMA)
In the frequency measurement of 1Hz.Preferred ingredient B is at least one copolymer, passes through styrene or α-methylstyrene (b1) it is obtained with acrylonitrile (b2) polymerization, i.e., so-called SAN- copolymer or AMSAN copolymer.San copolymer is more preferable 's.
SAN the and AMSAN copolymer is usually by 18 to 40 weight %, preferably 22 to 33 weight %, particularly preferred 25 to The acrylonitrile of 31 weight % and 82 to 60 weight %, preferably 78 to 67 weight %, the styrene of particularly preferred 75 to 69 weight % Or α-methylstyrene preparation, wherein styrene or α-methylstyrene and the summation of acrylonitrile are 100 weight %.
Component B, the especially described at least one SAN or AMSAN copolymer, it is preferable that its weight-average molar mass Mw is 85, 000-300,000g/mol, more preferable 120,000-250,000g/mol, most preferably 140,000-230,000 g/mol pass through Gel permeation chromatography measures and uses polystyrene calibration.Preferably, component B is at least two (preferably two kinds), three kinds, four Kind or five kinds of san copolymers mixture, wherein various san copolymers have different weight-average molar mass Mw (but in above-mentioned model In enclosing).
Copolymer B suspends in known manner by ontology, solution, and precipitating or emulsion polymerization obtain, preferably ontology, suspends And polymerisation in solution.The datail description of these polymerization processes is in such as " Plastics Handbook " (Eds.R.Vieweg and G.Daumiller)； " polystyrene " the 4th, Carl Hanser Verlag, Munich, 1996, from page 104；" modern styrene polymerization Object: polystyrene and styrol copolymer " "
(Eds., J.Scheirs, D.Priddy, Wiley, Chichester, UK, (2003), the 27-29 pages)；And GB-A 1,472,195.Melt volume rate (the MVR, according to ISO of component B (especially at least one san copolymer as defined above) 1133, under 220 DEG C and 10kg load) it is at least 3mL/10min, more preferably, in the range of 3 to 20mL/10min. Preferably, component B is at least two, three kinds, four kinds or five kinds copolymer B, the preferably mixture of san copolymer B, wherein various The MVR of copolymer is different, within the scope of 3-90mL/10min.At least two in component B, three kinds, four kinds or five kinds copolymers Selection will make the MVR of obtained mixture in the range of 3 to 20mL/10min.
Component C
Preferably, at least one (preferably a kind of) copolymer C, is made up of:
(c1) it is based on (C), 70-85% (weight) ethylene (c1),
(c2) it is based on (C), at least one (preferably a kind of) (methyl) acrylic acid C1-C6 Arrcostab of 15 to 30 weight % (c2), preferred C1-C6- alkyl acrylate, more preferable methyl acrylate, ethyl acrylate and/or n-butyl acrylate, it is optimal The methyl acrylate and/or ethyl propylene acid esters, especially methyl acrylate of choosing, and
(c3) it is based on (C), other comonomers that at least one of 0 to 10% weight can be copolymerized with (c1) and (c2) (c3), it is preferably selected from: carbon monoxide, alpha-olefin such as propylene and/or (methyl) acrylic acid, (methyl) glycidyl Ester.
(methyl) alkyl acrylate (c2) refers to the Arrcostab of acrylic or methacrylic acid.Acrylic or methacrylic The alkyl of acid esters can contain 1 to 6 carbon atom, particularly relate to methyl, ethyl, propyl, isopropyl, normal-butyl, sec-butyl, tertiary fourth Base, isobutyl group and isopentyl, preferred ester are methyl esters and ethyl ester.
Preferred copolymer C is made of ethylene (c1) and methyl acrylate (c2).
The copolymer C can be prepared by known methods, such as US 3, the method disclosed in 350,372, and the patent is public Content is opened to be hereby incorporated by reference.
Preferably, the melt flow rate (MFR) (MFR) of component C is 0.5-50g/10min (190 DEG C/2.16kg) (ASTM D1238；ISO 1133-1:2011), more preferable 0.5-10g/10min.The weight-average molar mass Mw of component C is usually less than 1, 000,000g/mol, preferably smaller than 700,000g/mol, more preferably less than 500,000g/mol.Suitable and preferred copolymer C commercially available fromElvaloyParticularly preferred Elvaloy AC ethylene-methyl acrylate, especially that A bit only containing ethylene and methacrylate unit.
Component D
Graft rubber copolymer D as described above is preferably made of following
(d1) it is based on (D), the graft bases (d1) of 12 to 20 weight %, and
(d2) it is based on (D), the graft (d2) of 80-88 weight % is grafted in graft base.
Graft rubber copolymer D preferably as described above, wherein component d23 is not present.Further preferably such as The upper graft rubber copolymer D, wherein component d11 is 1,3-butadiene.Grafting further preferably as described above Rubbery copolymer D, wherein component d12 is styrene.Graft rubber copolymer D further preferably as described above, wherein Component d21 is styrene.Graft rubber copolymer D further preferably as described above, wherein component d22 is acrylonitrile.
Graft rubber copolymer D more preferably as described above, is made up of:
(d1) D, 10 to 25 weight %, the preferably graft base (d 1) of 12 to 20 weight % are based on, system is made up of It is standby:
(d11) be based on d1, the 1,3-butadiene of 75 to 100 weight %, and
(d12) d1, the styrene of 0 to 25 weight % are based on；With
(d2) D, 75 to 90 weight %, the preferably graft (d2) of 80 to 88 weight % are based on, are grafted in graft base, And it comes from:
(d21) be based on d2,68 to 82 weight %, preferably 70 to 80 weight %, styrene, and
(d22) be based on d2,18 to, 32% weight %, preferably 20 to 30 weight %, acrylonitrile.
Graft base d1 can be linear polymer, long-chain branched polymer or star shape branch copolymer.Graft base d1 Usually soluble polymer, it is negligible without insoluble part or insoluble part.Comonomer d11 and d12 can unite With block form or in the form of a cone, (gradient of d11 and d12 form) polymerize in meter meaning.
It is preferred that obtaining grafting basis d1 by anionic polymerisation.
Bulk polymerization is preferably in individual media rather than carries out in water, usually using it is a series of two or more Flow reactor.Graft base (d1) is most often diene homopolymer or the copolymerization of polymerisation in solution preparation used in the method Object.In general, prepare graft base (d1) forms solution in monomer (d21) and (d22), then it is fed to reactor assembly.It can also A part of monomer (d21) and (d22) (the fresh and unreacted monomer from devolatilization) dissolution (d1) is used only, and will Remainder is added in reactor.
In Quality Process (mass process), as the polymerization of monomer (d21) and (d22) carry out, initially it is dissolved in Graft base (d1) in monomer mixture mutually separates appearance, and forms discrete rubber grain.The process is referred to as phase and turns Change, because continuous phase from rubber is transferred to graft rubber copolymer D in the course of the polymerization process.Special reaction device is anti-designed for control The inversion of phases part answered.Pass through the shear rate in control reactor, thus it is possible to vary rubber particle size is to optimize performance.It is some total Polycondensation monomer (d21) and (d22) are grafted on rubber grain.Reaction formula may include polymerization initiator, chain-transferring agent and other Additive.Diluent is occasionally used for reducing the viscosity of monomer and polymeric blends, to promote the processing of high conversion.The reaction It is preferred that being carried out in a manner of free radical solution polymerization.The product devolatilization of usual autoreactor system in future is to remove unreacted Monomer, be then granulated.Equipment for devolatilization includes that single screw rod and double screw extruder and flash distillation and film/chain steam Send out device.Unreacted monomer can be recycled and be recycled back into reactor to improve process yield.
Suspension polymerization generates the polymer of Partial Conversion and the mixture of monomer using quality reaction, between then using Suspension process of having a rest completes polymerization.When the conversion ratio of monomer completes about 15-30%, by the mixture of polymer and unreacted monomer It suspends in water and introduces suspending agent.The reaction was continued until reach the monomer conversion of height, then usually will be pulp centrifuged With unreacted monomer is removed before drying from product, obtain the product of beads form.The form of quality product suspension and Property is similar to the form and property of quality polymerizate.Some techniques that suspension polymerization remains water-base emulsion method are excellent Point, such as lower viscosity and good heat-removal capability in reactor.
When graft rubber copolymer D is obtained by free radical solution polymerization, at least one solvent, such as first are used Ethyl ketone, acetone, toluene and/or ethylbenzene.Preferably, the particle of graft rubber copolymer D is with 0.55 μm to 1.50 μm, preferably 0.60 μm to 1.00 μm of weight average particle diameter Dw.
Component E
Component E is at least one (preferably a kind of) inorganic additive selected from phyllosilicate (E1) and nanometer calcium carbonate (E2) E。
If there is component E1, the moulding compound being made of component A-D based on 100 parts by weight, usage amount is preferred It is 0.01 to 5pbw, more preferably 0.05 to 3pbw.
If there is component E2, the moulding compound being made of component A-D based on 100 parts by weight, usage amount is preferred It is 0.01 to 5pbw, more preferably 0.05 to 5pbw.
Component E1 is phyllosilicate.Suitable phyllosilicate is for example described in the inorganic chemistry religion of Hollemann Wiberg Section's book, 771-776 pages of Gruyter, Berlin, N.Y.1985, the of Walter de.
It is preferable to use serpentine type, such as centipede stone or siderite, kaolinite type, such as two pyroxenes, perlite or Pyroxene, pyrophyllite, the mica silicate from vermiculite group, illite group or montmorillonite/beidellite group, such as montmorillonite, or Mica or alumino-silicate, such as Moschus stone, phlogopite or biotite.Very particularly preferably mica.For the present invention, kaolinite Type includes kaolin, and essential mineral is kaolinite, and mica shape silicate includes bentonite, and essential mineral is montmorillonite.
According to the present invention, nanometer calcium carbonate (E2) refers to cium carbonate nanoparticles (NPCC), and average-size is less than 100nm, especially average-size are 15 to 60nm, and most preferably average particle size is about 40nm.The form of nano particle can be not Same shape, such as cube, spindle, stick or slice-shaped, preferably cube.
Suitable nanometer calcium carbonate can precipitate (HGCP) technology by high GRAVITY CONTROL and be obtained, and can be from NanoMaterialsIt is commercially available.
Component F
Other additives (being different from component E) and/or processing aid can be used as component F.
The example of this substance is lubricant, and release agent, wax, pigment, dyestuff, fire retardant, antioxidant resists light, fine Dimension or fleut, fiber or powdery reinforcing agent and antistatic agent effect stabilizer and other additives and they Mixture.
The example of suitable lubricant and release agent is stearic acid, stearyl alcohol, stearate, stearmide and silicone oil, Lignite wax and based on polyethylene or it is polyacrylic those.The moulding compound being made of component A-D based on 100 parts by weight, institute The dosage for stating lubricant and release agent is usually at most 3 parts by weight, preferably up to 2 parts by weight.
The example of pigment is organic and inorganic face of titanium dioxide, phthalocyanine, ultramarine blue, iron oxide and carbon black and whole class Material.For purposes of the invention, dyestuff is transparent, the translucent or opaque coloured any dyestuff that can be used for polymer, It is particularly suitable for those of coloring styrol copolymer dyestuff.This dyestuff is known to technical staff.Based on 100 parts by weight The moulding compound being made of component A-D, the dosage usually up to 20pbw, preferably up to 10pbw of the pigment and dyestuff.
The example of suitable fire retardant is antimony oxide (such as Sb2O3) and/or halogenated organic compounds.
Specially suitable antioxidant is the single or multiple core phenol antioxidant of steric hindrance, can have various take It can also be bridged for base and by substituent group.These include monomer and oligomeric compound, they can be by two or more Phenolic structure unit is constituted.Can also use quinhydrones or quinhydrones analog or its compound replaced, or based on tocopherol or its The antioxidant of derivative.Also the mixture of various antioxidants can be used.The usage amount of the usual antioxidant can be high Up to 1pbw, the moulding compound being made of component A to D based on 100 parts by weight.In principle, it is possible to using any commercially available Or the compound suitable for styrol copolymer.
It is used as together with example phenol antioxidant with above-mentioned, so-called co-stabilizer can be used simultaneously, especially It is phosphorous or sulfur-bearing co-stabilizer.These co-stabilizers containing P or S are known to technical staff and commercially available.
The example of suitable antioxidant has:
The ester of 3,5- di-t-butyl -4- hydroxyl phenylacetic acids and monohydric alcohol or polyalcohol, such as simultaneously preferred decyl alcohol, hendecane Alcohol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, 1,6- hexylene glycol, neopentyl glycol, 1, 9- nonanediol, ethylene glycol, diethylene glycol (DEG), triethylene glycol, pentaerythrite, 3- tiadenol, 3- pentadecanol, trimethylolpropane；
The ester of β-(3,5- di-tert-butyl-hydroxy phenyl)-propionic acid and above-mentioned monohydric alcohol or polyalcohol；With
The ester of β-(5- tertiary butyl-4-hydroxy -3- aminomethyl phenyl)-propionic acid and above-mentioned monohydric alcohol or polyalcohol；
The ester of β-(3,5- dicyclohexyl -4- hydroxy phenyl)-propionic acid and above-mentioned monohydric alcohol or polyalcohol.
Preferred antioxidant is 3,3'- thio-2 acid octacosane ester (CAS-No.693-36-7), octadecyl- The fourth of 3- (3,5- di-tert-butyl-hydroxy phenyl)-propionic ester (CAS-No.2082-79-3) and paracresol and bicyclopentadiene Glycosylation reaction product (CAS-No.68610-51-5).
Example for resisting the suitable stabilizers that shadow is rung is various substituted resorcinols, salicylate, benzo three Azoles, benzophenone and HALS (hindered amine light stabilizer), for example, those of can be commercially available Tinuvin.
Preferably 770 DF 1 of Tinuvin, bis- (2,2,6,6,-tetramethyl -4- piperidyl) sebacate (CAS- No.52829-07-9), Tinuvin P, 2- (2H- benzotriazole -2- base)-paracresol (CAS-No.2440-22-4), 3853,2,2,6,6- tetramethyl -4- piperidyl stearate (CAS-No.167078-06-0) of Cyasorb UV, Hostavin N 845 (CAS-No.86403-32-9) and its mixture.
The moulding compound being made of component A-D based on 100 parts by weight, the common dosage of stabilizer can be up to 2pbw。
Threadiness or the example of fleut are that (with glass fabric, glass isolator or glass fiber are thick for carbon fiber and glass fibre Yarn, staple glass, the form of bead) and wollastonite, particularly preferred glass fibre.When glass fibers are used, these glass Fiber can have the compatibility for having the dimensions and being aided with coupling agent to improve it with blend component.The glass fibre of incorporation can In the form of being short glass fiber, it is also possible to continuous strand (rove).Being made of component A-D based on 100 parts by weight Moulding compound, the common dosage of filler can be at most 20pbw, preferably up to 10pbw.
In the present invention, if without specifically mentioned, the usage amount of every kind of additive is usual amounts, therefore need not be in this side Face provides further details.
The preparation of moulding compound
The preparation of thermoplastic composition follows conventional method well known in the art.Preferably, component A to C and optionally Component D to F is squeezed out in conventional mixing apparatus (preferably in multi-cylinder grinding machine, mixing extruder or internal kneader) and is blended or matches It is mixed.
It is preferred that B, C and optional component D to F are mixed and are squeezed out at elevated temperatures, usually extremely at 150 DEG C by component A At a temperature of 300 DEG C.Producing, post-processing, during further processing and final molding, can by optional additive E and/or F is added in thermoplastic composition.Final molding can carry out on commercially available processing machine, and final molding includes for example Injection molding, sheet material squeeze out, optionally subsequent thermoforming, cold forming, the extrusion and calendering processing of tubing and profile.
Another aspect of the present invention is the moulded products made of thermoplastic composition.Thermoplastic composition can By various methods well known in the art as being molded, squeeze out, compression forming, vacuum forming, blow molding etc. forms moulded products.It is preferred that Moulded products be sheet material by being extruded into or squeeze out the layering sheet material of (coextrusion) formation by sheet layer.
The sheet material can be used for thermoforming, and can only be made of thermoplastic composition as described above, Huo Zheke With layer structure, wherein at least one cap rock is made of the moulding compound.
Another aspect of the present invention is the purposes of moulded products (especially thermoset sheet material), and the moulded products are by as above The thermoplastic composition is made, for cooling down the lining (liner) of equipment such as refrigerator.Thermoplasticity mould as described above Molding composition especially in the presence of HF hydrocarbon (HFO), shows to improve in the presence of aggressivity olefinic unsaturation foaming agent Environmental stress crack resistance (ESCR) and ABS material known to advantageous property, thus be suitable for manufacturing the heat of cooling equipment The lining of molding equipment.This lining includes the insulator of the mixture foaming with " forth generation " foaming agent or containing them.
Following embodiment and claim can further illustrate the present invention.
Embodiment
Graft rubber copolymer A
Prepare the a1 of graft base:
The graininess crosslinking fine grained rubber base-material for being used to prepare component A (emulsion graft polymerization rubbery copolymer) is in distillation (CAS-No.67701-06-8, C14-C18- saturated straight chain aliphatic monocarboxylic acid and C15-C18- are unsaturated straight for tallow acid Chain fatty race monocarboxylic acid) in the presence of, pass through the free-radical emulsion polymerization system of butadiene and styrene (monomer weight ratio 90/10) It is standby.Wherein, use potassium peroxydisulfate as initiator, temperature is 60 DEG C to 85 DEG C, and uses tetrasodium pyrophosphate as salt.
Addition initiator indicates the beginning of polymerization process.Finally, fine grained butadiene rubber latex is cooled to 50 DEG C Hereinafter, and lower than 50 DEG C at a temperature of in vacuum (200 to 500mbar) be partially removed in unreacted monomer, this meaning The end of polymerization process.
Solid content of starting styrenic/butadiene rubber (SBR) the rubber base-material so obtained with 41 weight %, 93% Rubber gels content (the line cage method in toluene), be one be derived from styrene and butadiene unit (weight ratio 10/ 90) rubber composition, weight average particle diameter are 0.08 μm and (are surveyed using the disc centrifuge of CPSInstruments by differential centrifugation It is fixed).Starting SBR is subjected to granularity increase with acetic anhydride in two batches, respectively obtains 0.25 μm and 0.55 μm of weight average particle diameter Dw value.
In order to obtain the agglomeration butadiene rubber latex that Dw is 0.25 μm, particulate butadiene rubber is provided first at 25 DEG C Latex, if it is desired, concentration and the stirring of 36 weight % are adjusted to deionized water.Temperature is risen to 40 DEG C, to the dispersion In in the form of aqueous mixtures be added 1.3 parts by weight acetic anhydride (the solid weight based on 100 parts of particulate butadiene rubber latex Amount), it is mixed with latex.Hereafter, it carries out agglomeration 10 minutes without stirring.
In form of an aqueous solutions by sulfonic acid polyelectrolyte anionoid dispersing agent (naphthalenesulfonic acid-formaldehyde condensate, CAS It 9084-06-04) is added in the latex of agglomeration, and is stirred.Then it is added to KOH as aqueous solution in the latex of agglomeration And it mixes by stirring.The solid content for the agglomeration butadiene rubber latex that Dw is 0.25 μm is 28.5 weight %.
In order to obtain the agglomeration butadiene rubber latex that Dw is 0.55 μm, particulate butadiene rubber is provided first at 25 DEG C Latex, if it is desired, concentration and the stirring of 33 weight % are adjusted to deionized water.Into the dispersion with the shape of aqueous mixtures The acetic anhydride (solid weight based on 100 parts of particulate butadiene rubber latex) of 2 parts by weight is added in formula, and mixes with latex. Hereafter, it carries out agglomeration 30 minutes without stirring.Sulfonic acid polyelectrolyte anionoid is dispersed in form of an aqueous solutions Agent (naphthalenesulfonic acid-formaldehyde condensate, CAS 9084-06-04) is added in the latex of agglomeration, and is stirred.Then KOH is made It is added in the latex of agglomeration and mixes by stirring for aqueous solution.The solid for the agglomeration butadiene rubber latex that Dw is 0.55 μm Content is 24.7 weight %.To have 0.25 μm (80 parts) and 0.55 μm (20 parts) of two kinds of latex to be mixed into rubber mass a1 In, the solid content with 26 weight %, in subsequent reaction step in the form of polymer emulsion.
Prepare graft rubber copolymer A:
Graft copolymer A is by 52 parts by weight of styrene/butadiene rubber (SBR), 34 parts by weight of styrene, 14 parts by weight third Alkene nitrile and cumene hydroperoxide, dextrose, ferrous sulfate, tert-dodecylmercaotan, isproportionated potassium rosinate connect through lotion Branch polymerization obtains.Firstly, above-mentioned SBR latex a1 is added, and temperature is risen to 70 DEG C.Styrene, acrylonitrile, tertiary dodecane is added Base mercaptan, the rosin acid potash soap and deionized water of disproportionation.At 70 DEG C, catalyst solution (sodium pyrophosphate, dextrose, hydrogen is added Cumene peroxide and the ferrous sulfate being dissolved in water).After the completion of addition, continue stirring 30 minutes, then cools down mixture.To Antiaging agent (such as antioxidant PL/Wingstay L, phenol, 4- first are added in the graft copolymer latex so obtained Base-, the reaction product with bicyclopentadiene and isobutene, CAS-No.68610-51-5), and under stiring add mixture Enter into the magnesium sulfate solution for be heated to 95 DEG C to be condensed.The product of condensation is washed with water and is dried, white is obtained The high rubber content resin combination of powder type.
Prepare substrate copolymer B
SAN- copolymer B1 is prepared by 72 weight % styrene and 28 weight % acrylonitrile through suspension polymerisation, weight average molar matter Amount is 230,000kg/mol (measured by gel permeation chromatography and use polystyrene calibration), and the value of MVR is 3.5cm3/ 10min (220 DEG C/10kg loads (ISO 1133-1:2011)).
SAN- copolymer B2 is prepared by 66 weight % styrene and 34 weight % acrylonitrile through suspension polymerisation, weight average molar matter Amount is 89,000kg/mol (measured by gel permeation chromatography and use polystyrene calibration), and the value of MVR is 75cm3/ 10min (220 DEG C/10kg loads (ISO 1133-1:2011)).
SAN- copolymer B3 is prepared by 66 weight % styrene and 34 weight % acrylonitrile through suspension polymerisation, weight average molar matter Amount is 180,000kg/mol (measured by gel permeation chromatography and use polystyrene calibration), and the value of MVR is 3cm3/ 10min (220 DEG C/10kg load (ISO 1133-1:2011)).
SAN- copolymer B4 is prepared by 69 weight % styrene and 31 weight % acrylonitrile through bulk polymerization, weight average molar matter Amount is 140,000kg/mol (measured by gel permeation chromatography and use polystyrene calibration), and the value of MVR is 19cm3/ 10min (220 DEG C/10kg load (ISO 1133-1:2011)).
SAN- copolymer B5 is prepared by 69 weight % styrene and 31 weight % acrylonitrile through suspension polymerisation, weight average molar matter Amount is 200,000kg/mol (measured by gel permeation chromatography and use polystyrene calibration), and the value of MVR is 4cm3/ 10min (220 DEG C/10kg loads (ISO 1133-1:2011)).
Graft rubber copolymer D (mABS):
In the presence of methyl ethyl ketone, by free radical solution polymerization, the Acrylonitrile Butadiene-Styrene copolymer D of continuous quantity is by 17% butadiene, and 63% Styrene, the preparation of 20% acrylonitrile, gel content are 30% (acetone method), and the weight average particle diameter of graft rubber is 0.6 to 1 μm (disc centrifuge of CPS Instruments is used to measure by differential centrifugation) and MVR is 5.5cm3/10min(ISO1133- 1:2011).
Gel content is measured (as dispersing agent) in acetone or toluene.About 0.25g polymer composition is dispersed in 20g 12-24 hours in dispersing agent, and gel phase and colloidal sol phase are separated at 20,000rpm, 25 DEG C with ultracentrifuge.It will separation Mutually dry, be calculate by the following formula gel content:
Gel=quality (gel phase)/(quality (gel phase)+quality (colloidal sol phase)) * 100 [%]
Prepare thermoplastic composition:
In the following Examples and Comparative Examples, above-mentioned copolymer A, B and D and following group are used by the amount provided in table 1 Divide C and F.The polymerization of 100 parts by weight is added in additive and processing aid (component F) by the amount (pbw) listed by left column in table 1 Object component.
Component C:AC1224: by the copolymer of a kind of ethylene and methyl acrylate of DuPont preparation, contain 24 weight % methyl acrylates；Melt flow rate (MFR): 2.0g/10min (190 DEG C/2.16kg, ISO 1133/ASTM D1238), Density: 0.944g/cm3(ASTM D792/ISO 1183), fusing point: 91 DEG C of DSC (ISO 3146/ASTM D3418), dimension card are soft Change point: 48 DEG C (ASTM D1525/ISO 306).
F1: ethylenebisstearamide, CAS-No.110-30-5
F2: silicone oil, 60,000cSt, dimethyl silicone polymer, CAS-No.63148-62-9
F3: thio energy heat stabilizer, 3,3'- thio-2 acid octacosane esters, CAS-No.693-36-7
F4: phenols primary anti-oxidant, octadecyl -3- (3,5- di-tert-butyl-hydroxy phenyl)-propionic acid
Ester, CAS-No.2082-79-3
F5: titanium dioxide, CAS-No.13463-67-7
The component A, B, C and D of table 1 and above-mentioned additive and processing aid F are compounded under the following conditions: extruder L/ D:30, diameter: 40mm, co-rotating twin screw, manufacture: KraussMaffei Berstorff, Germany, die head and fusing temperature Degree: 250 DEG C, yield: 50~60kg/h.
Thermoplastic compounds are tested using following methods:
Notch Charpy (Charpy) impact strength [kJ/m2]:
According to ISO 179-1A, sample (80 × 10 × 4mm, in 240 DEG C of mass-temperatures and the bet of 70 DEG C of mold temperature Modeling generates) notch charpy impact strength is measured at 23 DEG C.
Notched izod (Izod) impact strength [kJ/m2]:
According to ISO 180-1A, sample (80 × 10 × 4mm, in 240 DEG C of mass-temperatures and the bet of 70 DEG C of mold temperature Modeling generates) notched izod impact strength is measured at 23 DEG C.
Melt volume index (MVR [ml/10min]):
According to ISO 1133, Melt Volume Rate MVR is measured on polymer melt under 220 DEG C and 10kg load.
Break-draw strain [%]:
According to DIN EN ISO 527, dumb bell sample (170 × 10 × 4mm, in 240 DEG C of mass-temperatures and 70 DEG C of mould It is molded at a temperature of tool) break-draw strain [%] is measured at 23 DEG C.
ESCR method:
After mixing, obtained thermoplastic compounds are molded into the prod having a size of 80 × 10 × 4mm3.Injecting condition Are as follows: clamping force: 120MT, manufacturer: South Korea Dongcheng, injection temperature: 240 DEG C, injection speed: 60%, circulation time: 45 seconds, mould Tool temperature: 60 DEG C.It is tested according to following environmental stress crack resistance (ESCR), tests the chemical resistance of the molded bar:
The prod (80 × 10 × 4mm) of injection molding is mounted on fixture, the fixture is under the strain of 2.5% outer fiber The curvature kept constant.Fixture with test block is put into the tank equipped with chemical reagent, keeps prod completely capped.? During experiment, monitors and assess the degradation of ongoing sample at any time.Sample is set to place one under defined environmental condition The section specific time (usually 300 minutes or until complete crack) and by them after being taken out in fixture, check the object of degradation Reason state.
Measurement chemical resistance is assessed according to following optical index: complete crackle, partial crack, face crack, edge crack With the surface quality after aging.
Then test result (being shown in Table 2) is summarized with lower symbol:
X: it degenerates；▲: it is impacted very big；▲ ▲: is impacted；▲ ▲ ▲: somewhat impacted；▲ ▲ ▲ ▲: it is unaffected； (▲): 0.5 ▲
Table 1 describes the component of thermoplastic compounds.
For preferably more different materials, also sorted (all test materials of 1=(referring to table 2) to material Material with highest chemical resistance, all test materials of 2=have the material etc. of the second high chemical resistance).
For commonly using the test of chemicals such as pentamethylene, apply at room temperature.3,3,3- trifluoropropyl chloro- for anti-form-1- Alkene (19 DEG C of boiling point), test carries out at 0 DEG C to prevent reagent from evaporating, while the experimental condition kept constant.
By the thermoplastic of thermoplastic compounds Examples 1 and 2 according to the present invention and comparative example Cp well known in the prior art Property composition be compared, it can be found that invention Examples 1 and 2 thermoplastic composition shown during test it is excellent Different ESCR performance.The embodiment of the present invention 1 not only shows to the extraordinary resistance of anti-form-1-chloro-3,3,3 ,-trifluoropropene, But also show the excellent resistance to pentamethylene.This performance is critically important, because in most cases manufacturer is to make With the mixture of foaming agent.
The chemical resistance that the thermoplastic compounds of inventive embodiments 2 test foaming agent to two kinds is also very good.
The thermoplastic composition of the display embodiment of the present invention 1 of table 2 obtains optimal ESCR test result.The present invention Thermoplastic compounds (embodiment 1) 3,3,3- trifluoro propene chloro- to anti-form-1-and pentamethylene chemical resistance it is very good. This is critically important, because manufacturer in most cases uses the mixture of a variety of foaming agents.
In addition, inventive embodiments 1 show those known advantageous features of ABS material；Good processability (MVR, fracture Elongation), toughness (impact strength) and appearance (gloss).
In addition, the embodiment of the present invention 1 and 2 all shows advantageous property known to ABS material；Good processability (MVR, Elongation at break) and toughness (impact strength).

Claims (17)

1. the purposes that a kind of thermoplastic composition is used to have HF hydrocarbon domain of the existence, wherein the thermoplastic molding composition Object includes component A, B, C and optional D:
(A) the graft rubber copolymer A of 10-35 weight %, consisting of the following to be obtained through emulsion polymerization:
(a1) it is based on (A), at least one graft base (a1) of 30 to 90 weight % is prepared by following compositions:
(a11) it is based on (a1), at least one diene of 70 to 98 weight %, especially 1,3-butadiene, and
(a12) it is based on (a1), at least one monomer selected from the group below of 2 to 30 weight %: styrene, α-methylstyrene, third Alkene nitrile, methacrylonitrile and methyl methacrylate, especially styrene；With；
(a2) it is based on (A), the graft (a2) of 10 to 70 weight % is grafted in graft base and is prepared by following compositions:
(a21) it is based on (a2), at least one vi-ny l aromatic monomers of 65 to 95 weight %, especially styrene,
(a22) it is based on (a2), the acrylonitrile and/or methacrylonitrile of 5 to 35 weight %, preferably acrylonitrile, and
(a23) it is based on (a2), at least one monomer selected from the group below of 0 to 20 weight %: C1-C4- (methyl) acrylic acid alkyl Ester, maleic anhydride, N-phenylmaleimide, N- N-cyclohexylmaleimide and (methyl) acrylamide；
(B) at least one copolymer B of 50 to 70 weight %, is prepared by following compositions:
(b1) (B), at least one vi-ny l aromatic monomers of 50 to 95 weight %, optimization styrene or Alpha-Methyl benzene second are based on Alkene, more preferable styrene, and:
(b2) it is based on (B), the acrylonitrile and/or methacrylonitrile of 5 to 50 weight %, preferably acrylonitrile, and:
(b3) it is based on (B), one or more monomers as described in (a23) of 0 to 20 weight %；
(C) at least one copolymer C of 4 to 20 weight %, is prepared by following compositions:
(c1) it is based on (C), the ethylene of 70 to 91 weight %,
(c2) it is based on (C), a kind of at least one and preferred (methyl) acrylic acid C1-C6 Arrcostab of 9 to 30 weight %, preferably C1-C6 alkyl acrylate, more preferable methyl acrylate, ethyl acrylate and/or n-butyl acrylate, most preferably acrylic acid first Ester and/or ethyl acrylate, especially methyl acrylate, and
(c3) it is based on (C), other comonomers that at least one of 0-15 weight % can be copolymerized with (c1) and (c2) preferably select From: carbon monoxide, alpha-olefin such as propylene, and/or (methyl) acrylic acid, (methyl) glycidyl acrylate；
(D) at least one graft rubber copolymer D of 0 to 20 weight % is obtained by following groups of lease making bulk polymerizations:
(d1) it is based on (D), at least one graft base (d1) of 10 to 25 weight % is prepared by following compositions:
(d11) it is based on (d1), at least one diene of 75 to 100 weight %, especially 1,3-butadiene, and
(d12) (d1), at least one vi-ny l aromatic monomers of 0 to 25 weight %, optimization styrene or Alpha-Methyl benzene second are based on Alkene, more preferable styrene, and；
(d2) it is based on (D), the graft (d2) of 75 to 90 weight % is grafted in graft base and is prepared by following compositions:
(d21) be based on (d2), 68 to 82 weight %, preferably 70 to 80 weight %, at least one vi-ny l aromatic monomers, preferably Styrene or α-methylstyrene,
(d22) be based on (d2), 18 to 32 weight %, preferably 20 to 30 weight %, acrylonitrile or methacrylonitrile, preferred propylene Nitrile and
(d23) it is based on (d2), 0 to 20 weight %'s is one or more such as (a 23) described monomer；
The summation of wherein component A, B, C and D are weight 100%.
2. the purposes of thermoplastic composition according to claim 1, wherein the thermoplastic composition, is based on 100 The composition that parts by weight are made of component A, B, C and D, also other at least one additives comprising 0.01 to 20 parts by weight and/ Or processing aid F.
3. the purposes of thermoplastic composition according to claim 1 or 2, wherein the thermoplastic composition is further It include that at least one of the composition being made of component A, B, C and D based on 100 parts by weight, 0.01 to 10 parts by weight is selected from page The inorganic additive E of silicate (E1) and nanometer calcium carbonate (E2).
4. the purposes of thermoplastic composition as claimed in one of claims 1-3, wherein the thermoplastic molding composition Object includes component A, B, C and the D of following amount:
(A): 18 to 28 weight %；
(B): 55 to 75 weight %；
(C): 6 to 15 weight %；
(D): 0 to 15 weight %
5. the purposes of thermoplastic composition as claimed in one of claims 1-4, wherein the thermoplastic molding composition Object includes component A, B, C and the D of following amount:
(A): 10 to 35 weight %；
(B): 50 to 75 weight %；
(C): 4 to 20 weight %；
(D): 4 to 20 weight %.
6. the purposes of thermoplastic composition as claimed in one of claims 1-5, wherein graft copolymer A, by following Component is constituted:
(a1) 40 to 90 weight %, preferably 45 to 85 weight %, at least one graft base of particularly preferred 45 to 75 weight % A1 is made up of preparation:
(a11) be based on a1,80 to 98 weight %, preferably 85 to 97 weight %, at least one diene, preferred 1,3-butadiene, With
(a12) be based on a1,2 to 20 weight %, preferably 3 to 15 weight %, at least one monomer, optimization styrene；With；
(a2) 10 to 60 weight %, preferably 15 to 55 weight %, graft (a2), be grafted in graft base and by following Ingredient preparation:
(a21) 65 to 80 weight %, especially 65 to 75 weight %, at least one vi-ny l aromatic monomers (a21), especially Styrene, and
(a22) 35% weight % of 20to, especially 25 to 35 weight %, acrylonitrile and/or methacrylonitrile (a22), and
(a23) at least one monomer (a23) of 0 to 20 weight %；
7. the purposes of thermoplastic composition as claimed in one of claims 1-6, wherein copolymer B is by following components structure At:
(b1) 60 to 82 weight %, the preferably styrene or α-methylstyrene of 67 to 78 weight %, more preferable styrene, and
(b2) 18 to 40 weight %, preferably 22 to 33 weight %, acrylonitrile.
8. the purposes of thermoplastic composition as claimed in one of claims 1-7, the wherein weight average molar matter of copolymer C Mw is less than 1,000,000g/mol for amount, and preferably smaller than 700,000g/mol.
9. the purposes of thermoplastic composition as claimed in one of claims 1-7, wherein the MFR of copolymer C is 0.5- 50 [g/10min] (190 DEG C/2.16kg load, according to ASTM D1238；ISO 1133-1:2011).
10. the purposes of thermoplastic composition as claimed in one of claims 1-9, copolymer C is ethylene-acrylic acid first Ester copolymer.
11. the purposes of thermoplastic composition as claimed in one of claims 1-10, wherein graft copolymer D is by following Composition:
(d1) graft base (d1) of 12 to 20 weight %, is made up of preparation:
(d11) 1,3-butadiene of 75 to 100 weight %, and
(d12) styrene of 0 to 25 weight %；With
(d2) graft (d2) of 80 to 88 weight %, is grafted in graft base, and prepared by following compositions:
(d21) be based on (d2), 68 to 82 weight %, preferably 70 to 80 weight %, styrene, and
(d22) be based on (d2), 32% weight % of 18to, preferably 20 to 30 weight %, acrylonitrile.
12. the purposes of any one of -11 thermoplastic composition according to claim 1, wherein based on 100 parts by weight by The composition of component A, B, C and D composition, the content of component E1 are 0.01-5 parts by weight.
13. the purposes of any one of -11 thermoplastic composition according to claim 1, wherein based on 100 parts by weight by The composition of component A, B, C and D composition, the content of component E2 are 0.01-10 parts by weight.
14. the purposes of any one of -13 thermoplastic composition according to claim 1, wherein described thermoplastic moulded group It closes object and moulded products, especially sheet material or layering sheet material is formed by extrusion or co-extrusion.
15. the purposes of any one of -14 thermoplastic composition according to claim 1 is used as interior in cooling equipment Lining.
16. the thermoplastic composition as described in any one of claim 5-13.
17. thermoplastic composition according to claim 16, component A, B, C and D comprising following amount:
(A): 18 to 28 weight %；
(B): 55 to 70 weight %；
(C): 6 to 15 weight %；With
(D): 6 to 15 weight %.
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